Liquid pre-mix concentrates comprising two or more active ingredients are useful in a wide variety of agricultural applications. For example, two or more pesticidal active ingredients may be combined in order to control a wider spectrum of pests, or to utilize multiple modes of action, compared to the individual active ingredients alone.
Water insoluble pesticide active ingredients may be formulated in water as aqueous suspension concentrates (SC) or by dissolving the water insoluble pesticide in an organic solvent and forming an emulsifiable concentrate (EC). The preparation of these liquid, pre-mix concentrates can be challenging owing to chemical and/or physical instability issues.
Emulsifiable concentrate formulations, also known as emulsion concentrates or ECs, are widely used in crop protection. The disadvantages of some emulsifiable concentrates include their poor cold temperature stability and the pronounced tendency of the active ingredient to crystallize, owing to the low solubility of some active ingredients in the concentrate. It was an object of the present disclosure to provide an emulsifiable concentrate which overcomes these disadvantages.
Some aspects of the invention provide fungicidal compositions comprising: a fungicidal compound of the Formula:
at least one ionic surfactant; at least one nonionic surfactant; an acetate ester; and an N,N-dialkylcarboxamide.
In certain embodiments, the described fungicidal composition may include at least one additional fungicidal compound.
In certain embodiments, the acetate ester and the N,N-dialkylcarboxamide together form a water immiscible organic solvent for the described fungicidal composition.
In certain embodiments, the described fungicidal composition forms a stable, homogenous emulsifiable concentrate that readily emulsifies and forms a stable emulsion without crystallization of the fungicidal compound when added to water.
In certain embodiments, the described composition may include an adjuvant that improves the fungicidal performance of the composition.
In certain embodiments, the described composition may include additional active ingredients and/or inert formulation ingredients.
Also provided herein is a method of controlling plant derived fungal pathogens or diseases comprising contacting the vegetation or an area adjacent thereto to prevent the growth of the fungal pathogens or diseases with a fungicidally effective amount of a fungicidal composition comprising: a fungicidal compound of the Formula:
at least one ionic surfactant; at least one nonionic surfactant; an acetate ester; and an N,N-dialkylcarboxamide.
A first set of embodiments of the present disclosure includes fungicidal compositions comprising:
a) a fungicidal compound of the Formula

b) at least one ionic surfactant;
c) at least one nonionic surfactant;
d) at least one acetate ester; and
e) at least one N,N-dialkylcarboxamide.
A second set of embodiments includes the fungicidal compositions of the first set of embodiments, wherein the composition includes:                a) from about 1 gram per liter (g/L) to about 200 g/L of the fungicidal compound of the Formula        
                b) from about 1 g/L to about 100 g/L of the at least one ionic surfactant, wherein the at least one ionic surfactant includes at least one anionic surfactant;        c) from about 1 g/L to about 200 g/L of the at least one nonionic surfactant;        d) from about 50 g/L to about 700 g/L of the at least one acetate ester; and        e) from about 25 g/L to about 300 g/L of the at least one N,N-dialkylcarboxamide, wherein the at least one N,N-dialkylcarboxamide includes an N,N-dimethyl fatty acid amide.        
A third set of embodiments includes the fungicidal composition of any of the first and/or the second set of embodiments, wherein the composition includes from about 1 gram per liter (g/L) to about 200 g/L of the fungicidal compound of the Formula:

A fourth set of embodiments includes the fungicidal composition of any of the first through the third set of embodiments, wherein the composition includes from about 1 g/L to about 100 g/L of the at least one ionic surfactant, wherein the at least one ionic surfactant includes at least one anionic surfactant.
A fifth set of embodiments includes the fungicidal composition of any of the first through the fourth set of embodiments, wherein the composition includes from about 1 g/L to about 200 g/L of the at least one nonionic surfactant.
A sixth set of embodiments includes the fungicidal composition of any of the first through the fifth set of embodiments, wherein the composition includes from about 50 g/L to about 700 g/L of the at least one acetate ester.
A seventh set of embodiments includes the fungicidal composition of any of the first through the sixth set of embodiments, wherein the composition includes from about 25 g/L to about 300 g/L of the at least one N,N-dialkylcarboxamide, wherein the at least one N,N-dialkylcarboxamide includes at least one of an N,N-dimethyl fatty acid amide.
An eighth set of embodiments includes the fungicidal composition of any of the first through the seventh set of embodiments, wherein the at least one acetate ester and the at least one N,N-dialkylcarboxamide together form a water immiscible organic solvent.
A ninth set of embodiments includes the fungicidal composition of any of the first through the eighth set of embodiments, wherein the weight ratio of the at least one acetate ester:the at least one N,N-dialkylcarboxamide ranges from about 1-10:1-10.
A tenth set of embodiments includes the fungicidal composition of any of the first through the ninth set of embodiments, wherein the weight ratio of the at least one acetate ester:the at least one N,N-dialkylcarboxamide ranges from about 1-5:1-2.
An eleventh set of embodiments includes the fungicidal composition of any of the first through the tenth set of embodiments, wherein the at least one acetate ester is selected from a group consisting of benzyl acetate, cyclohexylmethyl acetate and phenyl acetate.
A twelfth set of embodiments includes the fungicidal composition of any of the first through the eleventh set of embodiments, wherein the at least one N,N-dialkylcarboxamide is selected from a group consisting of N,N-dimethylhexanamide, N,N-dimethyloctanamide, N,N-dimethyldecanamide and N,N-dimethyldodecanamide.
A thirteenth set of embodiments includes the fungicidal composition of any of the first through the twelfth set of embodiments, further including at least one additional fungicidal compound.
A fourteenth set of embodiments includes the fungicidal composition of the thirteenth set of embodiments, wherein the at least one additional fungicidal compound is selected from a group consisting of azoxystrobin, bifujunzhi, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, enoxastrohin, fenaminstrobin, fenoxystrobin, flufenoxystrobin, fluoxastrobin, jiaxiangjunzhi, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, triclopyricarb, trifloxystrobin, methyl 2-[2-(2,5-dimethylphenyloxymethyl)phenyl]-3-methoxyacrylate, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, imazalil, pefurazoate, prochloraz, triflumizole, pyrimidines, fenarimol, nuarimol, pyrifenox, and triforine.
A fifteenth set of embodiments includes the fungicidal composition of the thirteenth and/or the fourteenth embodiments, wherein the at least one additional fungicidal compound is selected from a group consisting of azoxystrobin, kresoxim-methyl, picoxystrobin, pyraclostrobin, trifloxystrobin, epoxiconazole, fenbuconazole, myclobutanil, propiconazole, prothioconazole, and tebuconazole.
A sixteenth set of embodiments includes the fungicidal composition of any one of thirteenth through the fifteenth set of embodiments, wherein the at least one additional fungicidal compound is selected from a group consisting of pyraclostrobin, prothioconazole and propiconazole.
A seventeenth set of embodiments includes the fungicidal composition of any of the first through the sixteenth set of embodiments, further including an adjuvant that improves the fungicidal performance of the composition selected from a group consisting of a non-ionic surfactant, a polyether modified organopolysiloxane and an alkyl phosphonate.
An eighteenth set of embodiments includes methods of controlling fungal plant pathogens or diseases comprising the steps of contacting the vegetation or an area adjacent thereto to prevent the growth of the fungal pathogens or diseases with a fungicidally effective amount of a fungicidal composition comprising:
a) a fungicidal compound of the Formula

b) at least one ionic surfactant;
c) at least one nonionic surfactant;
d) at least one acetate ester; and
e) at least one N,N-dialkylcarboxamide.
A nineteenth set of embodiments includes the methods of the eighteenth set of embodiments, wherein the fungicidal composition includes from about 1 gram per liter (g/L) to about 200 g/L of the fungicidal compound of the Formula

A twentieth set of embodiments includes the methods of the eighteenth and/or the nineteenth set of embodiments, wherein the fungicidal composition includes from about 1 g/L to about 100 g/L of an anionic surfactant of the at least one ionic surfactant, wherein the at least one ionic surfactant includes at least one anionic surfactant.
A twenty first set of embodiments includes the methods of any of the eighteenth through the twentieth set of embodiments, wherein the fungicidal composition includes from about 1 g/L to about 200 g/L of the at least one nonionic surfactant.
A twenty second set of embodiments includes the methods of any of the eighteenth through the twenty first set of embodiments, wherein the fungicidal composition includes from about 50 g/L to about 700 g/L of the acetate ester.
A twenty third set of embodiments includes the methods of any of the eighteenth through the twenty second set of embodiments, wherein the fungicidal composition includes from about 25 g/L to about 300 g/L of the at least one N,N-dialkylcarboxamide, wherein the at least one N,N-dialkylcarboxamide includes an N,N-dimethyl fatty acid amide.
A twenty fourth set of embodiments includes the method of any of the eighteenth through the twenty third set of embodiments, wherein the at least one acetate ester and the at least one N,N-dialkylcarboxamide together form a water immiscible organic solvent.
A twenty fifth set of embodiments includes the methods of any of the eighteenth through the twenty fourth set of embodiments, wherein the weight ratio of the at least one acetate ester:the at least one N,N-dialkylcarboxamide ranges from about 1-10:1-10.
A twenty sixth set of embodiments includes the methods of any of the eighteenth through the twenty fifth set of embodiments, wherein the weight ratio of the at least one acetate ester:the N,N-dialkylcarboxamide ranges from about 1-5:1-2.
A twenty seventh set of embodiments includes the methods of any of the eighteenth through the twenty sixth set of embodiments, wherein the at least one acetate ester is selected from a group consisting of benzyl acetate, cyclohexylmethyl acetate and phenyl acetate.
A twenty eighth set of embodiments includes the methods of any of the eighteenth through the twenty seventh set of embodiments, wherein the at least one N,N-dialkylcarboxamide is selected from a group consisting of N,N-dimethylhexanamide, N,N-dimethyloctanamide, N,N-dimethyldecanamide and N,N-dimethyldodecanamide.
A twenty ninth set of embodiments includes the methods of any of the eighteenth through the twenty eighth set of embodiments, wherein the water immiscible organic solvent includes benzyl acetate and one or more than one of a fatty acid N,N-dialkylcarboxamide.
A thirtieth set of embodiments includes the methods of any of the eighteenth through the twenty ninth set of embodiments, the fungicidal composition further comprising at least one additional fungicidal compound.
A thirty first set of embodiments includes the methods of any of the thirtieth set of embodiments, wherein the at least one additional fungicidal compound is selected from a group consisting of azoxystrobin, bifujunzhi, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, enoxastrobin, fenaminstrobin, fenoxystrobin, flufenoxystrobin, fluoxastrobin, jiaxiangjunzhi, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, triclopyricarb, trifloxystrobin, methyl 2-[2-(2,5-dimethylphenyloxymethyl)phenyl]-3-methoxyacrylate, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, imazalil, pefurazoate, prochloraz, triflumizole, pyrimidines, fenarimol, nuarimol, pyrifenox, and triforine.
A thirty second set of embodiments includes the methods of any of the thirtieth through the thirty first set of embodiments, wherein the at least one additional fungicidal compound is selected from a group consisting of azoxystrobin, kresoxim-methyl, picoxystrobin, pyraclostrobin, trifloxystrobin, epoxiconazole, fenbuconazole, myclobutanil, propiconazole, prothioconazole, and tebuconazole.
A thirty third set of embodiments includes the methods of any of the thirtieth through the thirty second set of embodiments, wherein the at least one additional fungicidal compound is selected from a group consisting of pyraclostrobin, prothioconazole and propiconazole.
A thirty fourth set of embodiments includes the methods of any of the eighteenth through the thirty third set of embodiments, the fungicidal composition further comprising an adjuvant that improves the fungicidal performance of the fungicidal composition selected from a group consisting of a non-ionic surfactant, a polyether modified organopolysiloxane and an alkyl phosphonate.
A thirty fifth set of embodiments includes the methods of any of the eighteenth through the thirty fourth set of embodiments, wherein the fungal plant pathogens include Septoria tritici, Puccinia triticina, Mycosphaerella graminicola, Puccinia triticina, Puccinia striiformis, Venturia inaequalis, Ustilago maydis, Uncinula necator, Rhynchosporium secalis, Leptosphaeria nodorum, Magnaporthe grisea, Monilinia fructicola, Pseudoperonospora cubensis, Pseudocercosporella herpotrichoides, Phakopsora pachyrhizi, Phaeosphaeria nodorum, Blumeria graminis tritici, Blumeria graminis hordei, Erysiphe cichoracearum, Ezysiphe graaminis, Glomerella lagenarium, Cercospora beticola, Alternaria solani, Rhizoctonia solani, Plasmopara viticola, Phytophthora infestans, Pyricularia oryzae, and Pyrenophora teres. 
A thirty sixth set of embodiments includes the methods of any of the eighteenth through the thirty fifth set of embodiments, wherein the fungal plant diseases include anthracnose, blasts, botrytis, brown rust, blister smut, brown rot, downy mildew, fusarium, powdery mildew, rusts, glume blotch, leaf blotch, net blotch, sheath blight, stripe rust, scab, eye spot, leaf spot, early blight, and late blight.
A thirty seventh set of embodiments includes the compositions or methods of any of the eighteenth through the thirty sixth set of embodiments, wherein the at least one ionic surfactant is an anionic surfactant selected from a group consisting of an alkali, alkaline earth and ammonium salt of an alkylarylsulfonic acid.
A thirty eighth set of embodiments includes the compositions or methods of any of the eighteenth through the thirty seventh set of embodiments, wherein the at least one nonionic surfactant is selected from a group consisting of an alcohol initiated EO/PO block copolymer and an alcohol ethoxylate.
A thirty ninth set of embodiments includes fungicidal compositions comprising:
a) a fungicidal compound of the Formula

b) a calcium salt of an alkylaryl sulfonate;
c) an alcohol initiated EO/PO block copolymer;
d) a tridecyl alcohol ethoxylate;
e) a polyether modified organopolysiloxane;
f) benzyl acetate; and
g) an N,N-dimethyl fatty acid amide.
A fortieth set of embodiments includes fungicidal compositions comprising:
a) a fungicidal compound of the Formula

b) prothioconazole;
c) a calcium salt of an alkylaryl sulfonate;
d) an alcohol initiated EO/PO block copolymer;
e) a tridecyl alcohol ethoxylate;
f) a polyether modified organopolysiloxane;
g) benzyl acetate; and
h) an N,N-dimethyl fatty acid amide.
A forty first set of embodiments includes fungicidal compositions comprising:
a) a fungicidal compound of the Formula

b) pyraclostrobin;
c) an calcium salt of an alkylaryl sulfonate;
d) an alcohol initiated EO/PO block copolymer;
e) a tridecyl alcohol ethoxylate;
f) a polyether modified organopolysiloxane;
g) benzyl acetate; and
h) an N,N-dimethyl fatty acid amide.